Inchoately marked articles of manufacture



Patented Sept. 8-, 1931 UNITED STATES PATENT OFFICE ERNEST H. HUNTRESS, OF MELROSE, MASSACHUSETTS, ASSIGNOR TO PLYMOUTH CORD- AGE COMPANY, OF PLYMOUTH, MASSACHUSETTS, A CORPORATION" OF MASSACHU- SETTS INCHOATELY MARKED ARTICLES 01 MANUFACTURE No Drawing.

This invention relates to improvements in inchoately marked articles of manufacture. More particularly it relates to the provision of a distinguishing device for a manufactured product of any sort that is not readily capable of being durably and distinctively marked by ordinary methods. The purpose is to provide so that the authenticity or idenful.

tity of a particular specimen of the product may be determined, to authenticate 01;, identify it as being of a certain origin, or as being made by a particular formula, or as having any other specific attribute which the device, if present, is known to signify, notwithstanding that the specimen under examination has passed out of the hands of its maker into commerce, and even may have passed through its industrial life to the verge of destruction. The invention will be herein described as it may be applied in connection with rope, this being a particular article of manufacture in which the utility of such a device is especially prominent, and for which the invention has been experimentally tested and found success- The customary marking device for identifying a rope, viz, the introduction of a distinctively colored yarn, has become so common, so readily counterfeited and so open to challenge as to its authenticity, that such yarns have ceased to. be a satisfactory marking means. I V For the needed invention to be of the desired practical value, the technique of practicing it must be simple. reliable and economical. That is, it should be capable of being performed quickly and by unskilled workmen; without complication of apparatus or of chemical manipulation; and Without serious interruption of or addition to the existing manufacturing processes for the article to which it is to be applied. It must be reliable both in the sense f giving results which are constantly repro ucible, under ordinary industrial conditions, and also in the sense-that the production of the ultimate results must not be impaired either by the deterioration which is incidental to age of the rope, nor by exposure of the rope to the usual incidents such as repeated flexure, abrasion, and gathering of dirt or absorption and evaporation Application filed February 29, 1928. Serial No. 258,134.

other hand be of such a nature that the characteristic results cannot be produced by other materials which may naturally be introduced into rope for special purposes, such as for lubrication, for water-proofing or for mildew-proofing. Obviously it is requisite that the treatment should not harm the strength or other qualities of the fibres or other material treated.

The invention, by the preliminary impregnating of a yarn, provides in the completed rope a permanent, inchoate mark which remains for any desired period during the marketing, industrial use and other life of the rope, until by the application of a suitable chemical reagent the inchoate mark becomes a finished mark of distinctive color aspect and of permanent character. In the form of the invention herein described, which isparticularly useful where theattribute of secrecy is desired, the inchoate form of the mark does not noticeably affect the appearance, the feeling or other characteristics of the yarn to which it is applied; and the in choate mark is indistinguishable by ordinary inspection of the rope.

In the particular method and materials here described for illustrating the invention the fundamental principle is that the color is produced in the fibre of the yarn by chemical reaction between twoseparate substances, one of which is already fast in the fibre. The rope is completed and becomes an article of commerce and of industrial use with the application of only the first component.-

This rope is a completely identifiable product. The particular system to which resort thereon and then the developer or second the rapidity with which they work.

component applied practically immediately or else the coloring of the fibre will be feeble, or fail altogether. The present invention proposes to use, for the first component of the dye, a substance which has such an ailinity for the fibre that by adsorption, penetration of the fibrecells, or otherwise, it adheres permanently. For this the arylamides of 2, 3 hydroxynaphthoic acid are available. instead of the difiicult development above mentioned, involving the diazotizing of the second component, the invention is practical for use in the field, without laboratory or dyeroom equipment, and without the skill of a chemist or the technique of a dyer, so that an unskilled person can detect the presence of the inchoate mark, because it employs as developer a salt which is es ecially prepared in permanently diazotized form. This may be one of the alkali salts of the nitrosamines of primary aromatic amines. In the present invention it is a unique feature that the combination of the first and second components of the dye does not occur during the preparation of the marker yarn, but is caused to take place only after the rope is complete and on an occasionin which all of the other yarns as well as that which is inchoatcly marked are together immersed in a solution, the second component, to which the inchoately marked yarn immediately responds by acquiring a color strikingly distinctive from that of the solution and from that which itself and the other yarns previously had and from that which the other yarns acquire by being immersed in the solution. The first component is here used therefore only to impregnate permanently the marker yarn, and preferably not to impart color or to produce any other visible change therein, and the second component'is used months or years later to detect the presence of the first. The arylamides of 2, 3 hydroxynaphthoic acid, suggested as the first component, are available commercially as AS Naphthols. Their importance for the present invention over all other types of phenols or naphtholic substances is due to their unique property of possessing great affinity for the fibres,such as manila, sisal, etc., used in rope, before the formation of any azo dye stuff by reaction with the second component has taken place. The alkali salts of the nitrosamines of primary aromatic amines, suggested as the second component, are available commercially as Fast Salts, the term fast signifying The other yarns of the rope, .not having been treated with the phenol, do not respond to the application of the Fast Salt, and remain unchanged in aspect, except for a slight color which they may acquire from the initial color of the solution of Fast Salt in water. This last is not the finished color produced by the reaction of the Fast Salt with the phenol.

And

It will thus be perceived that the invention by which the foregoing results are. attained is a species of the generic improvement which consists, in the case of rope, in providing a yarn which reacts differently from the way in which the other yarns react, when all together are subjected to a test treatment.

A description in detail of an illustrative instance of the practice of the invention follows:

The inchoate mark is prepared by brief immersion of an ordinary rope yarn, consisting of manila fibre and containing the usual oil, in a hot Water solution, containing, in addition to sulfonated castor oil (soluble oil) and an excess of free alkali, a small concentration (0.10O.25%) of an arylamide of 2,

3 hydroxylnaphthoic acid. A suitable formula for this solution is indicated by the following:

1.0 g Q-hydroxy 3-naphthoic anilide (Naphthol AS) 2.0 g soluble oil 4 2.0 g 23.5% sodium hydroxide solution diluted to 1000 c. c.

This gives a naphthol concentration of 0.109% and a free alkali concentration of 0.03%. Variations may be made. A considerable number of naphthols of the AS series are available and all of the series appear to possess marked afiinity for the fibre, thisnot being limited to manila hemp, but being true of cotton and other; but there is a difference in the deepness of the color ultimately obtained by development, this being greatest with naphthol AS/BO, Q-hydroxy 3-naphthoic alphanaphthalide which has greatest atfinity for the fibre, but being satisfactory with naphthol AS Which has much less atfinity but is less expensive. The concentration may vary. Even at a naphthol concentration of 0.05% and an immersion of ten seconds the color ultimately developedis sufficiently deep to serve as a distinguishing marker. In fact, however, the duration of immersion does not make such difference, thediminution of depth of shade obtained with decreasing time of immersion being not considerable, in the solution of lower concentration, Whether the immersion were sixty seconds or two seconds. The rate of penetration of the naphthol into the fibre increases with temperature. The use of soluble oil maintains a satisfactory homogeneity of solution and during the preparation of the naphthol solution its presence markedly facilitates the mixing of the dry powder with the alkali. Its presence however does not affect the ultimate color produced nor perceptibly increase the natural penetrating power of the alkaline solution. The presence of excess alkali prevents hydrolysis of the naphthol salt and resultant precipitation of the free naphthol itself; but if the alkali be present in excess of a certain minimum representing alkali equivalent to the naphthol used, the degree of its excess does not appear to affect the shade of color developed. The deleterious effect of the free alkali on the fibre has been found to beentirely negligible as shown by tensile strength tests. When thus impregnated some of the AS naphthol s possess so great an afiinity for the rope fibre that even after short pieces of made up rope containing the impregnated yarn had been shakenfo-r one hundred hours with sea water or ordinary water the,inchoately marked yarn still responded satisfactorily to the. developing treatment. The inchoate mark is made by the simple process for running a regular yarn which is later to be incorporated in the rope, or other article, that is to be marked, through a bath of the above solution or such variation of it as may be desired, with such brief period of immersion as may be'found convenient. Preferably this yarn will be allowed to dry before it is incorporated in the rope, in order to prevent the solution which is wet upon it from being to some extent transferred to a neighboring yarn as would happen if it were incorporated in the rope while wet, but the drying is not a necessary part of the process of rendering the yarn sensitive to development into a permanent color. A rope having been made according to ordinary or any suitable method, or the other article, whatever it may be, having been made, incorporating one or more of the treated yarns or other elements, the article is complete and goes into commerce and industry. In the greater numher of instances in practical life this is as far as the article will ever go toward having a mark of the nature under discussion. The complete article is characterized by having the mark in inchoate condition. a

In any instance in which it ,is desired, and atany period of time afterward, even years, and in. any place however remote from factory or laboratory, the inchoate mark may be developed into a finished mark. Under laboratory conditions it is possibleito carry out the development by the use of diazotized solution of m-nitro p-toluidine base as developer, the diazonium salts being obtained by the carefully regulated action of nitrous and hydrochloric acids upon the various color bases. But for practical commercial and industrial life wherein convincing and certain and quick test is requisite, which can be applied by a person unskilled in chemistry or in the technique of dyeing, it is preferable to use for the developer 1 stabilized form of these diazonium salts, such being obtainable commercially, among materials used for manufacturing azo dyes, as colored powders which are easily soluble and in addition to the actual diazonium salts contain a large quantity of some inorganicmaterial such as zinc chloride which effects the stabilization of the materials. One commercial variety is known under the commercial name of Fast Salts, further designated usually by some color as red, orange, scarlet, blue, black. The development of the inchoate marker to the color produced by the particular dye stuff can then be effected by dissolving a little of the developer in a tumbler of water, and immersing an end of the rope in the solution. The color appears in a few seconds, in the yarn which is the inchoate mark, the other yarns remaining unaffected by the characteristic reaction, although there may be a slight change of color in another direction. For example, upon using an inchoate marker prepared by impregnation resulting from ten seconds immersion in a 0.10% naphthol AS solution containing 0.18% sodium hydroxide and 1% soluble oil, and using Fast Blue Salt B (a chemical. name for which is stabilized tetrazotized dianisidine) for development,

satisfactory results are obtained, whether the yarn acquires a deep reddish blue, while the,

other yarns in the rope at the same time change from their characteristic hemp color to a pale pink, giving excellent contrast.

If it were desired that instead of this element of secrecy there should be an indication as to which is the treated yarn the invention can equally be applied, For example, the marker yarn might be preliminarily dyed some distinctive color or might be distinguished by difference of material; or might be simultaneously dyed distinctively by a dye suitable for that purpose and impregnated by the naphthol AS solution, but in this case it would be desirable to choose a dye having an aflinity for the fibre approximating that of" marking is possible to be obtained in a single.

yarn by the use of the present invention by the selection of a naphthol, for example naphthol AS/BR (a chemical name for which is Beta-hydroxy-naphthoic acid dianisidide) which particular naphthol possesses a very brilliant yellow fluorescence in ultra violet light, although another naphthol, as for example, naphthol AS/BS shows no fluorescence while others show a pale yellow fluorescence of no particular importance.

In the rope or other article which is marked the developed marker herein described may be associated with ordinary or other markers, embodied in other yarns, the use of which is not precluded, and the aspect of which does not undergo the characteristic change when immersed in the developing solution.

While the disclosed herein as it may be applied to a yarn of rope, by impregnation of the yarn through an immersing of it in solution, the invention is not limited to that material nor to that method of application of the solution or the developer.

It is intended that the patent shall cover by suitable expression in the appended claims, whatever features of patentable novelty exist in the invention herein disclosed in relation to the provision of an inchoate mark and its development into a finished mark.

The invention claimed is: 1. A new article of manufacture consisting of an industrial product havingincorporated therein, in undeveloped form, a developable naphthoic substance the characteristics of which constitute potential indentifying means and include a strong aflinity for the material of the product in which it is incorporated, said undeveloped naphthoic substance being capable, despite the lapse of a long period of time, of manifesting its presgnce by reacting chemically into developed orm. a.

2. A new article of manufacture consisting of an industrial product having incorporated therein, in undeveloped form, a developable naphthoic substance the characteristics of which constitute potential iden tifying means and include a strong aflinity for the material of the product in which it is incorporated, said ,undeveloped naphthoic substance being capiflgle, despite the lapse of a long period of time, of manifesting its presence by reacting chemically into developed form when brought into contact with a diazotized reactant.

-' 3. A new article of manufacture comprising an industrial product having incorporated therein, in undeveloped form, one of the aryl amides of 2, 3 hydroxynaphthoic acid, the characteristics of which amide constitute potential identifying means and include a strong affinity for the material of the product in which it is incorporated; said undeveloped amide being capable, despite the lapse of along period of time after its being so incorporated, of manifesting its presence in said product by reacting chemically into deve oped form when brought into contact with a diazotized reactant.

Signedat Boston, Massachusetts, this thirtieth day of January 1928.

ERNEST H. HUNTRESS. 

